权利要求：
1.-17. (canceled)
18. A process for the production of a three-dimensional object, the external area of which comprises at least one area section which is produced in that an area section in two-dimensional form is first produced by means of an additive manufacturing process (layer-by-layer shaping process) on a flat base plate, comprising the following steps:
I) applying at least one hardenable polymer or hardenable reactive resin in flowable form in the form of lines of material onto a flat base plate by means of a layer-by-layer shaping process for the production of a first layer;
II) applying a second layer onto the first layer, produced by means of a layer-by-layer shaping process;
III) optionally applying from 1 to 198 further layers produced as in step II), where respectively a new layer is applied onto the respective preceding layer;
IV) hardening of the layers;
V) separating the hardened area section from the flat base plate; and
VI) molding the hardened area section to give a three-dimensional object by means of deep-draw or thermoforming;
where at least one layer is produced via application of at least one hardenable polymer or hardenable reactive resin in flowable form in the form of lines of material onto the respective substrate with respectively a modulus of elasticity in the cured state of ≥500 MPa in accordance with EN ISO 527-1 (latest issue dated April 1996, current ISO version of February 2012).
19. A process for the production of a three-dimensional object, the external area of which comprises at least one area section which is produced in that an area section in two-dimensional form is first produced by means of an additive manufacturing process (layer-by-layer shaping process) on a flat base plate, comprising the following steps:
i) applying at least one hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of ≥500 MPa in flowable form in the form of lines of material onto a flat base plate by means of a layer-by-layer shaping process for the production of a layer, where the layer provides a coherent area with or without cutouts;
ii) hardening of the layer;
iii) separating the hardened area section from the flat base plate; and
iv) molding of the hardened area section to give a three-dimensional object by means of deep-draw or thermoforming.
20. The process as claimed in claim 18, characterized in that a layer-by-layer shaping process is selected mutually independently from a group consisting of melt layering, fused filament fabrication, inkjet printing and photopolymer jetting.
21. The process as claimed in claim 18, where the lines of material are applied in the form of droplets onto the flat base plate or onto one of the layers that may already be present on the base plate.
22. The process as claimed in claim 18, characterized in that the discharge temperature of the substance mixtures from the nozzle in the steps I) to III) is in the range from 80° C. to 420° C.
23. The process as claimed in claim 18, characterized in that base plate has been heated and the heating temperature of the base plate is in the range from 20° C. to 250° C.
24. The process as claimed in claim 18, characterized in that a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of ≥500 MPa is selected from the group consisting of thermoplastic polyurethane, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, cycloolefinic copolyester, polyetheretherketone, polyetheramideketone, polyetherimide, polyimide, polypropylene, polyethylene, acrylonitrile-butadiene-styrene, polylactate, polymethyl, methacrylate, polystyrene, polyvinyl chloride, polyoxymethylene, polyacrylonitrile, polyacrylate, and celluloid.
25. The process as claimed in claim 18, characterized in that the same hardenable polymer or hardenable reactive resin is used in all of the layers.
26. The process as claimed in claim 18, characterized in that at least one layer comprises another hardenable polymer and hardenable reactive resin.
27. The process as claimed in claim 18, characterized in that a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of ≥500 MPa is used in all of the layers.
28. The process as claimed in claim 18, characterized in that a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of <500 MPa is used in at least one layer.
29. The process as claimed in claim 28, characterized in that a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of <500 MPa is used in the first layer.
30. The process as claimed in claim 28, characterized in that a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of <500 MPa is used in the final layer.
31. The process as claimed in claim 18, characterized in that the three-dimensional object is a cellphone shell, a housing, where said item has a 3D profile, packaging or an item of furniture with surface structures, an A, B or C column, a roof module or a dashboard of an automobile, a seat shell, a filter basket, a medical product such as a rigid corset or an orthosis, a protector, a damping element or a lightweight structure with framework structure.
32. The process as claimed in claim 18, where the first layer is applied to an interlay, for example a textile or a foil, which transfers the surface shape of the flat base plate to the first layer of a process of the invention, and to which the lines of material of the first layer bond, so that this interlay becomes part of the area section and thus also part of the three-dimensional object.
33. A process for the production of a protector designed appropriately for a user, comprising the steps of:
a) determining the relevant body-region-geometry data of the user;
b) calculating to convert the 3D-body-geometry data for the production of an area section;
c) manufacturing a three-dimensional object in a process as claimed in claim 18, where step VI) or, respectively, step iv), the three-dimensional shaping, takes place via deep-draw or thermoforming in accordance with the body-region-geometry data of the user from step a).
34. A protector obtained by the process as claimed in claim 18.
发明内容：
[0007]The invention is based on the discovery that by use of topological methods it is possible to transform many components with large surface area and with thin external walls mathematically into a coherent “two-dimensional” form. The topology of a three-dimensional object can easily be produced via molding of the two-dimensional form with respectively individually appropriately designed structure.
[0008]A first aspect provides a process of the invention for the production of a three-dimensional object, the external area of which comprises at least one area section which is produced in that an area section in two-dimensional form is first produced by means of an additive manufacturing process (layer-by-layer shaping process) on a flat base plate, comprising the following steps:[0009]I) application of at least one hardenable polymer or hardenable reactive resin in flowable form in the form of lines of material onto a flat base plate by means of a layer-by-layer shaping process for the production of a first layer;[0010]II) application of a second layer onto the first layer produced by means of a layer-by-layer shaping process, preferably by means of the layer-by-layer shaping process as in step I);[0011]III) optionally application of from 1 to 198 further layers produced as in step II), where respectively a new layer is applied onto the respective preceding layer;[0012]IV) hardening of the layers;[0013]V) separation of the hardened area section from the flat base plate; and[0014]VI) molding of the hardened area section to give a three-dimensional object by means of deep-draw or thermoforming;
where at least one layer is produced via application of at least one hardenable polymer or hardenable reactive resin with a modulus of elasticity in the cured state of ≥500 MPa in accordance with EN ISO 527-1 (latest issue dated April 1996, current ISO version of February 2012) in flowable form in the form of lines of material on the respective substrate.
[0015]An embodiment provides a process of the invention for the production of a three-dimensional object, the external area of which comprises at least one area section which is produced in that an area section in two-dimensional form is first produced by means of an additive manufacturing process (layer-by-layer shaping process) on a flat base plate (5), comprising the following steps:[0016]I) application of at least one hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of ≥500 MPa in accordance with EN ISO 527-1 (latest issue dated April 1996, current ISO version of February 2012) in flowable form in the form of lines of material onto a flat base plate by means of a layer-by-layer shaping process for the production of a first layer;[0017]II) application of a second layer onto the first layer produced by means of a layer-by-layer shaping process, preferably by means of the layer-by-layer shaping process as in step I);[0018]III) optionally application of from 1 to 198 further layers produced as in step II), where respectively a new layer is applied onto the respective preceding layer;[0019]IV) hardening of the layers;[0020]V) separation of the hardened area section from the flat base plate; and[0021]VI) molding of the hardened area section to give a three-dimensional object by means of deep-draw or thermoforming.
[0022]A second aspect provides a process of the invention for the production of a three-dimensional object, the external area of which comprises at least one area section which is produced in that an area section in two-dimensional form is first produced by means of an additive manufacturing process (layer-by-layer shaping process) on a flat base plate, comprising the following steps:[0023]i) application of at least one hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of ≥500 MPa in accordance with EN ISO 527-1 (latest issue dated April 1996, current ISO version of February 2012) in flowable form as lines of material onto a flat base plate, by means of a layer-by-layer shaping process for the production of a layer, where the layer provides a coherent area with or without cutouts (for example in the shape of a honeycomb);[0024]ii) hardening of the layer;[0025]iii) separation of the hardened area section from the flat base plate; and[0026]iv) molding of the hardened area section to give a three-dimensional object by means of deep-draw or thermoforming.
[0027]A preferred embodiment of the two aspects and their preferred embodiments provide a process of the invention where the layer-by-layer shaping process is melt layering (fused filament fabrication (FFF)), inkjet printing or photopolymer jetting.
[0028]Another preferred embodiment of the first aspect and its preferred embodiments provides a process where the layer-by-layer shaping process in step I) is melt layering (fused filament fabrication (FFF)), inkjet printing or photopolymer jetting.
[0029]Another preferred embodiment of the second aspect and its preferred embodiments provide a process where the layer-by-layer shaping process in step i) is melt layering (fused filament fabrication (FFF)), inkjet printing or photopolymer jetting.
[0030]Another preferred embodiment of the first aspect and its preferred embodiments provides a process where the layer-by-layer shaping process in step I) and II) and III) is respectively the same and is selected from the group consisting of melt layering (fused filament fabrication (FFF)), inkjet printing and photopolymer jetting.
[0031]Another preferred embodiment of the two aspects and their preferred embodiments provides a process where the discharge temperature of the substance mixtures from the nozzle in the steps I) to II) is in the range from 80° C. to 420° C.
[0032]Another preferred embodiment of the two aspects and their preferred embodiments provides a process where the base plate has been heated and the heating temperature of the base plate is in the range from 20° C. to 250° C.
[0033]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where a hardenable polymer or hardenable reactive resin with a modulus of elasticity in the cured state of ≥500 MPa is selected from a group consisting of thermoplastic polyurethane (TPU), polycarbonate (PC), polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cycloolefinic copolyester (COC), polyetheretherketone (PEEK), polyetheramideketone (PEAK), polyetherimide (PEI) (e.g. Ultem), polyimide (PI), polypropylene (PP) and polyethylene (PE), acrylonitrile-butadiene-styrene (ABS), polylactate (PLA), polymethyl methacrylate (PMMA), polystyrene (PS), polyvinyl chloride (PVC), polyoxymethylene (POM), polyacrylonitrile (PAN), polyacrylate, and celluloid preferably selected from a group consisting of TPU, PA, PEI, and PC, particularly preferably from a group selected from TPU and PC.
[0034]Another preferred embodiment of the two aspects and their preferred embodiments provides a process where the same hardenable polymer or hardenable reactive resin is used in all of the layers.
[0035]Another preferred embodiment of the first aspect and its preferred embodiments provides a process where at least one layer comprises another hardenable polymer or hardenable reactive resin.
[0036]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of ≥500 MPa is used in all of the layers.
[0037]Another preferred embodiment of the first aspect and its preferred embodiments provides processes where a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of <500 MPa is used in at least one layer.
[0038]Another preferred embodiment of the first aspect and its preferred embodiments provides processes where a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of <500 MPa is used in the first layer.
[0039]Another preferred embodiment of the first aspect and its preferred embodiments provides processes where a hardenable polymer or hardenable reactive resin with respectively a modulus of elasticity in the cured state of <500 MPa is used in the final layer.
[0040]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where at least one hardenable polymer or hardenable reactive resin is used for the application of a layer in the form of a flowable and hardenable substance mixture.
[0041]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where at least one hardenable polymer or hardenable reactive resin is used for the application of a layer in the form of at least two different flowable and hardenable substance mixtures.
[0042]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where the hardening is achieved via cooling of thermoplastics, via low- or high-temperature polymerization, via polyaddition, polycondensation, addition or condensation, or via polymerization initiated by electromagnetic radiation.
[0043]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where the hardening is achieved via a UV or IR light source placed immediately downstream of an injection nozzle (3).
[0044]Another preferred embodiment of the two aspects and their preferred embodiments provides processes where the three-dimensional object is a cellphone shell, a housing, e.g. of an electrical item, where said item has a 3D profile, packaging or an item of furniture with surface structures, an A, B or C column, a roof module or a dashboard of an automobile, a seat shell, a filter basket, a medical product such as a rigid corset or an orthosis, a protector, a damping element or a lightweight structure with framework structure.
[0045]A preferred embodiment of the first aspect and its preferred embodiments provides a process where a plurality of the individual lines of material are deposited in lateral direction or in the direction of application of the lines of material of the first layer with different thickness.
[0046]Another preferred embodiment of the two aspects and their preferred embodiments provides a process where at least one hardenable polymer or hardenable reactive resin is used for the application of a layer in the form of a flowable and hardenable substance mixture or where at least one hardenable polymer or hardenable reactive resin is used for the application of a layer in the form of at least two different flowable and hardenable substance mixture(s), where the substance mixtures comprise at least one filler selected from the group consisting of reinforcing fibers selected from polyamide fibers, glass fibers, carbon fibers or aramid fibers, or comprise reinforcing particles selected from inorganic or ceramic nano powders, metal powders or plastics powders or carbon black, and comprise organic and inorganic pigments.
[0047]Another preferred embodiment of the first aspect or of one of its other preferred embodiments provides a process where a line of material of a layer has only partially hardened when lines of material of a new layer are applied onto said layer, and the final hardening takes place together with the hardening of the line(s) of material deposited thereover.
[0048]Another aspect provides a process for the production of a protector appropriately designed for a user comprising the steps of:[0049]a) determination of the relevant body-region-geometry data of the user;[0050]b) calculation to convert the 3D-body-geometry data for the production of an area section in accordance with steps I) to V) or i) to iii) in accordance with a process of aspect one or two;[0051]c) manufacture of a three-dimensional object in a process as claimed in any of claims 1 to 13, where step VI) or, respectively, step iv), the three-dimensional shaping, takes place via deep-draw or thermoforming in accordance with the body-region-geometry data of the user from step a).
[0052]The expressions body-region-geometry data and 3D-body-geometry data are used synonymously.
[0053]Another aspect provides a protector obtainable by a process of the invention.
[0054]The indefinite article “a/an” generally means “at least one”, i.e. “one or more”. The person skilled in the art will understand that in particular situations the meaning must be “one”, i.e. “1” and, respectively, that in an embodiment the indefinite article “a/an” also concomitantly comprises “one” (1).
[0055]All of the preferred embodiments described herein for a process of the invention or a product produced by a process of the invention can be combined with one another, as long as they do not contravene laws of nature.
3D Printing Processes
[0056]The expression “additive manufacture” is known to the person skilled in the art and is the generic expression for various processes for the rapid production of sample components on the basis of design data.
[0057]The expression “layer-by-layer shaping processes using flowable/flowable and hardenable substance mixtures” as used herein preferably refers to FFF, but can also refer to any other known 3D printing processes using flowable and hardenable substance mixtures, e.g. photopolymer jetting (http://www.custompartnet.com/wu/jetted-photopolymer; as at Apr. 8, 2015) or inkjet printing processes (http://www.custompartnet.com/wu/ink-jet-printing; as at Apr. 8, 2015).
[0058]The expression “fused filament fabrication” (FFF; melt layering, also sometimes called plastic jet printing (PJP)) as used herein means a manufacturing process which derives from the additive manufacturing sector and which can construct a workpiece layer-by-layer from a fusible plastic. FIG. 1 is a diagram of a setup for a FFF process. The plastic can be used with or without further additions such as fibers. Machines for FFF are classed as 3D printers. This process uses heating to liquefy a plastics or wax material in the form of wire. The material solidifies when it is finally cooled. The material is applied by extrusion, using a heated nozzle which can be moved freely in relation to a manufacturing plane. Possibilities here are either that the manufacturing plane is fixed, the nozzle being freely movable, or that a nozzle is fixed and a substrate table (with a manufacturing plane) can be moved, or that both elements, nozzle and manufacturing plane, can be moved. The velocity at which the substrate and nozzle can be moved in relation to one another is preferably in the range from 1 to 60 mm/s. The layer thickness is, as required by each application, in the range from 0.025 to 1.25 mm; the discharge diameter of the stream of material (nozzle outlet diameter) from the nozzle is typically at least 0.05 mm. The individual layers in layer-by-layer model production thus bond to give a complex part. A product is usually constructed in that an operating plane is repeatedly traversed line-by-line (formation of a layer), and then the operating plane is displaced upward “to form a stack” (formation of at least one further layer on the first layer), so that a molding is produced layer-by-layer.
[0059]The design of the nozzle here is preferably such that quantities of material can be dispensed either continuously or in droplet form. It is preferable that the quantities of material are dispensed in droplet form.
[0060]It is preferable that in the 3D printing process in the present process of the invention the nozzle is over the flat base plate (when the first layer is applied) or over previously applied layers at a distance corresponding to from 0.3 to 1 times the diameter of the material filament to be applied (nozzle outlet diameter), preferably from 0.3 to 0.9 times, for example from 0.3 to 0.8 times, from 0.4 to 0.8 times or from 0.5 times to 0.8 times. This correlation between distance of the nozzle from the substrate (substrate being either the flat base plate or a previously applied layer) and nozzle outlet diameter ensures that the material is forced on to the substrate with a certain applied pressure and better adhesion is thus produced between the layers of the resultant area section.
[0061]The substance mixtures used in the process of the invention are heated, shortly upstream of the nozzle or in the nozzle, to at least 75° C., and thus rendered flowable. The person skilled in the art is aware of the temperature ranges required to render known amorphous polymers/thermoplastics flowable. The temperature to which the liquefied substance mixtures are heated, this also being the discharge temperature of the substance mixtures from the nozzle, is in the range from 80° C. to 420° C., preferably from 120° C. to 400° C. (for example from 160° C. to 400° C.), more preferably in the range from 180° C. to 360° C.
[0062]In a process of the invention, a liquefied substance mixture is applied to the flat base plate through the nozzle in the form of lines of material for the production of a first layer, which consists of individual lines of material running parallel to one another; or consists of a coherent area made of lines of material bonded to one another, or consists of geometric figures formed by lines of material in honeycomb form or in another form. A line of material here can consist either of a continuous filament of material or of a plurality of filaments of material (e.g. individual droplets) which are applied alongside one another on the operating plane in a manner such that they flow into one another and thus form a continuous line of material. The viscosity of the substance mixture here after it leaves the nozzle in the form of line of material is sufficiently high to prevent uncontrolled flow of the resultant line.
[0063]As already described elsewhere, it is preferable that the line of material is applied in the form of droplets to the base plate or to a layer previously applied. Processes particularly suitable for the application of the polymer or reactive resin are jetted photopolymer and inkjet printing. The distance between adjacent droplets deposited here can be sufficiently small to permit formation of a coherent structure therefrom, an example being a geometric figure taking the form of a honeycomb or taking another form.
[0064]The person skilled in the art is aware of the viscosities/line diameters required in a process such as FFF, jetted photopolymer or inkjet printing.
[0065]By use of the ratio of distance between nozzle and substrate to filament diameter (proportional to the nozzle outlet diameter and velocity of the material) it is possible, through flattening (and thus broadening) of the stream of material discharged from the nozzle (a continuous filament of material or a plurality of filaments of material discharged in succession from the nozzle which then coalesce), to produce, through the application of the lines of material, either a coherent area or lines of material separated from one another by uncovered areas. If the first layer consists of lines of material which are not in lateral contact with each other, and if in the following step a second layer is applied onto the first layer, there must be points of contact (e.g. points of intersection) or areas of contact between the two areas in order to ensure that the two layers adhere to one another. In this case, in a process of the invention, the area covered by a first layer is defined via the second layer applied onto the first layer. In a case where a first layer has been applied in the form of lines of material parallel to one another, and a second layer has been applied to the first layer, either the value of the angle of the direction of application (quantitative value associated with the direction of application) of the lines of material of the second layer is ≠0°, based on the direction of application of the lines of material of the first layer (thus permitting formation of pores by the two layers) or the direction of application of the lines of material of the second layer is the same as the direction of application of the lines of material of the first layer, but the lines of material of the second layer are displaced by about half of the distance, preferably half of the distance, between the centers of the lines of material of adjacent lines of material of the first layer. Each line of the second layer here must have a width at least sufficient to bring about contact between said line and the two lines of the first layer that are respectively situated under said line. The displacement of the lines of material ensures, through the bonding of the two layers to one another, continuous bonding (no formation of pores).
[0066]A preferred embodiment of the present invention provides a process and, respectively, a three-dimensional object produced by a process of the invention, where at least two layers together form pores, where the size of the pores formed by these at least two layers is from 0.3 times to 1000 times the maximal line thickness of two layers forming the pore. In a preferred embodiment, the size of a pore is from 0.3 times to 5 times the maximal line thickness of two layers forming the pore.
[0067]By way of example, the distance between the nozzle, for example in an FFF process, and the substrate (flat base plate, interlay or previously printed layer), and the distance of the lines of material from one another during the formation of a (new) layer, can be selected in a process of the invention in such a way that no coherent area is formed during the formation of a (new) layer, but instead all of the layers of the area section are composed of parallel lines of material. The angle of the direction of application of the lines of material forming a layer here is ≠0° for two successive layers, based on the direction of application of the first of the two layers. It is preferable that the angle of the direction of application in the case of at least two successive layers is in the range from 30° to 150°, for example in the range from 45° to 135° or in the range from 60° to 120° or in the range from 85° to 95° or 90°. The person skilled in the art will understand that variations of up to ±5° can occur in the direction of application of the lines of material of a second layer onto a first layer because, by virtue of the mutually parallel lines of material of the substrate layer, the surface of the substrate for the second layer naturally exhibits local unevenness.
Flat Base Plate
[0068]Flat base plates for additive manufacturing processes are known to the person skilled in the art. A flat base plate can be produced by a conventional or generative technique; by way of example, a base plate can be milled so that it has the advantages of accurate dimensions and shape, and also very good surface quality. There are many different materials available for milling, an example being ureol, wood or aluminum. For a particular geometry it can be advisable to produce the base generatively, for example by means of laser sintering.
[0069]A flat base plate serves for the shaping of the surface of the area section produced in a process of the invention. Accordingly, a first layer can be applied in a process of the invention directly onto a flat base plate; alternatively, there can be an interlay present, for example a textile or a foil, which transfers the shape of the surface of the flat base plate to the first layer of a process of the invention, where the first layer is applied on said interlay and the lines of material of the first layer bond to said interlay, and therefore this interlay becomes part of the area section and thus also part of the three-dimensional object.
[0070]The surface of the flat base plate preferably consists of glass, carbon, polypropylene, or stainless steel, or of a surface coated with Teflon or with polyimide, etc.; alternatively, said surface is specifically provided with an adherent primer layer which promotes adhesion of the objects to be printed on the surface, thus minimizing distortion of the desired objects to be printed. The adherent layer here is typically a low-melting-point compound which may be predissolved in a suitable solvent. The person skilled in the art is aware of a very wide variety of adhesion promoters.
[0071]A “flat base plate” for the purposes of the present invention is a substrate which is in essence flat in the operating plane and on which the first layer of an area section is applied in a production process of the invention. “Essentially flat” means that a substrate is fixed in an XY-plane of a Cartesian coordinate system with three axes X, Y and Z (Z then being 0), and exhibits no deviation on the Z-axis, or exhibits only slight deviation thereon, caused by material (see, for example, FIG. 2). Deviations in Z-direction for a plane defined in XY-direction are preferably at most 3 mm, more preferably at most 1 mm, but it is still more preferable that the deviations in Z-direction of the surface are at most twice the maximal layer-application thickness of a first layer (but at most 3 mm, preferably at most 1 mm); it is particularly preferable that the deviations in Z-direction of the surface are smaller than the maximal layer-application thickness of a first layer, where the size of the flat base plate in its orthogonal dimensions in an imaginary XY-plane is respectively greater at least by a factor of 5, preferably by a factor of 10, with preference by a factor of 50, with more preference by a factor of 100, than the maximal deviation in the Z-plane. By way of example, the diameter of a round, flat base plate with a height difference of 2 mm is at least 1 cm, at least 2 cm, at least 10 cm or at least 20 cm; if a flat base plate is square, the length of the edges forming the base plate is respectively at least 1 cm, 2 cm, 10 cm or 20 cm.
[0072]The shape of a flat base plate is irrelevant, as long as the base plate has a flat area which serves as substrate for a first layer of an area section, and as long as said base plate is, in all of its X- and Y-directions, larger than or as large as the area of the first layer of a two-dimensional area section of the present invention. The shape of the base plate can be symmetrical, e.g. round, rectangular, square, etc., or asymmetrical.
[0073]In a preferred embodiment, the flat base plate can be heated in order to delay premature hardening of the material via temperature-related solidification of the first layer. The temperature to which the base plate is heated is preferably in the range from 20° C. to 250° C., for example from 30° C. to 250° C., or for example in the range from 40° C. to 200° C., for example from 60° C. to 200° C. or from 60° C. to 150° C. However, the temperature to which the flat base plate is heated should not be above the nozzle-discharge temperature used in a process of the invention for a to provide flowability to the flowable and hardenable substance mixture. It is preferable that the heating temperature is at least 10° C. below the nozzle-discharge temperature.
[0074]Heating of the flat base plate is preferably continued at least until, after conclusion of the application of the first layer of the area section, at least one second layer has been applied onto the first layer.
Substance Mixtures
[0075]A hardenable polymer or hardenable reactive resin for the purposes of the present invention can be used alone or in the form of “flowable and hardenable substance mixtures” in a process of the invention. The expression “flowable and hardenable substance mixtures” accordingly refers to a substance mixture comprising at least one hardenable polymer or at least one hardenable reactive resin—preferably a thermoplastic—and at least one additional substance, for example fibers, UV hardeners, peroxides, diazo compounds, sulfur, stabilizers, inorganic fillers, plasticizers, flame retardants and antioxidants. In particular in the case of reactive resins, mixtures of two or more reactive resins can have been mixed in advance, or are mixed on the substrate. In the latter case it is possible by way of example that application takes place from different nozzles. The flowable and hardenable substance mixtures can differ in their nature, but must, under the conditions of the process of the invention, be low- or high-viscosity extrudable plastics compositions or liquid printable plastics compositions. These can be thermoplastics, silicones, unvulcanized rubber or else hardenable reactive resins (preferred product of hardened reactive resins being a thermoplastic).
[0076]Thermoplastics can by way of example be thermoplastic polyurethane (TPU), polycarbonate (PC), polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cycloolefinic copolyester (COC), polyetheretherketone (PEEK), polyetheramideketone (PEAK), polyetherimide (PEI) (e.g. Ultem), polyimide (PI), polypropylene (PP) and polyethylene (PE), acrylonitrile-butadiene-styrene (ABS), polylactate (PLA), polymethyl methacrylate (PMMA), polystyrene (PS), polyvinyl chloride (PVC), polyoxymethylene (POM), polyacrylonitrile (PAN), polyacrylate, and celluloid preferably selected from a group consisting of TPU, PA, PEI, and PC, particularly preferably from a group selected from TPU and PC.
[0077]The flowable and hardenable substance mixtures and, respectively, hardenable polymers or hardenable reactive resins in a process of the invention can be polymers and/or polymerizable oligomers and, respectively, monomers with or without additional substances, e.g. polyamide, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Kevlar fibers, glass fibers, aramid fibers or carbon fibers, rayon, cellulose acetate, and/or commonly used natural fibers (e.g. flax, hemp, coir, etc.). The substance mixtures can also comprise, alongside or instead of fibers, reinforcing particles, in particular selected from inorganic or ceramic nano powders, metal powders or plastics powders, for example made of SiO2 or Al2O3, AlOH3, carbon black, TiO2 or CaCO3. Substance mixtures can moreover comprise by way of example peroxides, diazo compounds and/or sulfur.
[0078]Preferred hardenable polymers or hardenable reactive resins or flowable and hardenable substance mixtures comprising a hardenable polymer or hardenable reactive resin, where these are used in a process of the invention, consist of/comprise thermoplastic polymers or reactive resins which react to give a thermoplastic.
[0079]Preference is in particular given to substance mixtures in a process of the invention comprising/consisting of thermoplastic polyurethane (TPU), polycarbonate (PC), polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cycloolefinic copolyester (COC), polyetheretherketone (PEEK), polyetheramideketone (PEAK), polyetherimide (PEI) (e.g. Ultem), polyimide (PI), polypropylene (PP) and polyethylene (PE), acrylonitrile-butadiene-styrene (ABS), polylactate (PLA), polymethyl methacrylate (PMMA), polystyrene (PS), polyvinyl chloride (PVC), polyoxymethylene (POM), polyacrylonitrile (PAN), polyacrylate, and celluloid. Particular preference is given to substance mixtures comprising/consisting of TPU, PA, PEI, or PC; very particular preference is given to substance mixtures comprising/consisting of TPU or PC.
[0080]In a particularly preferred embodiment, a process of the invention uses, as flowable and hardenable substance mixtures or hardenable polymers, TPU, PC, PA, PVC, PET, PBT, COC, PEEK, PEAK, PEI, PP, PE, PAN, ABS, PLA, PMMA, PS PVC, POM, PAN, polyacrylate or celluloid (preferably TPU, PC, PA or PEI, particularly preferably TPU or PC) in the form of filament, pellets or powder. In another preferred embodiment, these flowable and hardenable substance mixtures made of TPU, PC, PA, PVC, PET, PBT, COC, PEEK, PEAK, PEI, PP, PE, PAN, ABS, PLA, PMMA, PS PVC, POM, PAN, polyacrylate or celluloid (preferably TPU, PC, PA or PEI, particularly preferably TPU or PC) additionally comprise fibers (e.g. glass fibers) and/or reinforcing particles, possible fibers being both short fibers <2 mm and long fibers >2 mm. It is also possible to use “continuous-filament fibers” which continue throughout the entire length of an applied line of material. The presence of fibers during the extrusion of the flowable and hardenable substance mixture in a process of the invention leads to